CN104797326B - Process and apparatus for heat integrated liquid absorbent regeneration through gas desorption - Google Patents

Process and apparatus for heat integrated liquid absorbent regeneration through gas desorption Download PDF

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Publication number
CN104797326B
CN104797326B CN201380060680.XA CN201380060680A CN104797326B CN 104797326 B CN104797326 B CN 104797326B CN 201380060680 A CN201380060680 A CN 201380060680A CN 104797326 B CN104797326 B CN 104797326B
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liquid
film
steam
gas
product stream
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CN104797326A (en
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P·费龙
L·T·沃德豪
A·J·卡曾斯
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Commonwealth Scientific and Industrial Research Organization CSIRO
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Commonwealth Scientific and Industrial Research Organization CSIRO
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B01D53/268—Drying gases or vapours by diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/104—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons
    • B01D2257/7025—Methane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/20—Capture or disposal of greenhouse gases of methane

Abstract

A process and apparatus for stripping a gas from a gas-rich liquid. The apparatus includes a desorption unit (10) to desorb a gas from the gas-rich liquid to form a first product stream (13) including the gas and a vapour, and a second product stream (14) including a gas-lean liquid. The desorption unit (10) includes a gas-rich liquid inlet (25), a first product stream outlet, and a second product stream outlet. The apparatus further includes at least one of a membrane condenser (22) and/or a membrane (evaporator17). The membrane condenser (22) includes a membrane interface (26) permeable to the vapour through which vapour transfers from the first product stream to the gas-rich liquid stream and the membrane evaporator (17) includes a membrane interface (18) permeable to the vapour through which vapour transfers to separate a vapour portion from the second product stream (14), and an outlet for a vapour reduced second product stream.

Description

For the technique and equipment of heat integration liquid-absorbant regeneration are carried out by gas desorption
Invention field
The present invention relates to a kind of for improving the energy efficiency of gas stripping (gas stripping) and absorbent regeneration Method and apparatus, and CO is stripped in particular to from liquid-absorbant2。
Background of invention
In this specification to the reference of any prior art it is not, and is not construed as, recognizes or in any form Imply that the prior art constitutes a part for common sense in Australian or any other national jurisdiction, or it is described Prior art reasonably can be expected to be determined by one skilled in the art, understand and be considered related.
CO is separated from flue gas in power station, cement kiln and steel production2These industrial activities are allowed to be continuing with fossil fuel, Reduce most important greenhouse gases i.e. CO simultaneously2Discharge.Although being currently developed for separating CO from flue gas2It is some not With technique, but the use of the chemical absorption process of the aqueous solution of chemical absorbent is dominant technology, it is advanced that this is mainly due to which State of development.Although it is in low CO2Remove capacity under be it is feasible, but it and not up to large-scale industry operation it is required Scale.Therefore the scale for expanding technique is a significant challenge.Show in Fig. 1 CO is carried out using chemical absorbent2Reclaim Typical process flow diagram.
After cooling, flue gas 100 is made to contact with the chemical absorbent in absorber 102.Air blast 103 is needed in gas Body through after the cooler 104 that temperature is typically in 40 DEG C and 60 DEG C is transported the gas pump through absorber, borrows This CO2Combined by the chemical absorbent in absorber 102 afterwards.After through absorber 102, flue gas is through water washing section 113 so that water balance in system, and remove entrained steam any drop and after leave absorber 102.Then Will be containing chemically combined CO2" richness " absorbent solution the top of stripper 107 is transported to via 105 pump of heat exchanger.In height Under warm (100 DEG C to 140 DEG C), under the pressure between 1 bar and 2 bars, the regeneration of chemical absorbent is carried out in stripper 107. Stripper 107 is the gas/liquid contactor for making rich absorbent contact with the steam produced in reboiler 108.
Heat is supplied to reboiler 108 to maintain regeneration condition.This can cause because heated solution is to provide desorption chemical With reference to CO2The energy cost caused by desorption heat needed for producing with the steam for serving as stripping gas.By Steam Recovery cold In condenser 109 and it is recycled to stripper 107, and CO2Product gas 110 leave condenser 109.Cool down in cooling water or air The heat of condensate is taken away in device.CO2Product 110 be it is relatively pure (>99%) product, wherein vapor are main other groups Point.Due to the selectivity properties of chemical absorption process, the concentration of inert gas is low.Then will be containing few CO2" lean " Absorbent solution 111 is via lean-rich heat exchanger 105 and 112 pump of cooler is transported back to absorber 102 so which drops to absorption Device temperature levels.CO2Clearance is typically 90% or so.
The energy requirement of chemical absorption process is essentially from the heat for being supplied to reboiler 108.The heat is for from lean Solution 106 produces the steam for serving as stripping gas, i.e. the heat makes CO2Partial pressure remain sufficiently low to carry for desorption technique For driving force.Steam is also the carrier of thermal energy, and by the condensation of steam, it discharges desorption CO2With heating by desorber 107 Chemical absorbent needed for energy.The amount of the steam generated in reboiler 108 should keep as low as possible, but some steam are always Inevitably with the CO for producing2It is lost in from desorption unit together, and this represents energy loss, because steam is generally cold Coalescence and energy is pulled away in cooling water.
Need to propose a kind of technique and equipment than current process more Energy Efficient.It has been proposed that various in prior art Method.
WO 2007/075466 discloses a kind of method, wherein the lean chemical absorbent left from the bottom of desorber is sent The lower flash vessel of pressure is balanced to pressure ratio.Barren solution has low CO2Partial pressure；Therefore the steam produced by is mainly steam. The stripping and heating that the chemical absorbent in desorber can be thought by vapor recompression and in being injected into desorption device is carried For other steam.This needs to add two pieces equipment：Flash vessel and compressor.Which increase capital and operating cost.In addition, adding Plus other compressor increased total energy consumption-therefore impair energy-conservation, this is undesirable.
US 4152217 is disclosed by using heat exchanger, by carrying out heat with the rich absorbent solution into desorber Exchange from the CO for leaving desorber2/ vapour mixture extracts heat energy to recycle heat.This allows the potential of condensate Heat is recovered as the sensible heat amount in rich absorbent.Rich absorbent stream is needed to split into two however, the religious doctrine of this patent shows Plume, this is complicated from for technological process and control angle.
US 4444571 discloses a kind of method for reclaiming potential heat from gas/steam mixture, and methods described is used Compared to the film of the selectively permeable steam of other gases contained in mixture.The penetrant for mainly containing steam is pressed again Contracting, and the penetrant is injected in the base segment of desorber.Although suitable film is obtainable, the technique Extra energy is needed, this is undesirable.
Art methods for improving the energy characteristics of desorber be all it is limited because they address only it is single Improve step and assume common technology layout as shown in Figure 1.
Present invention aim to address at least some is above in previously mentioned shortcoming in prior art.
Summary of the invention
In the context of the present invention, Essential Terms " richness " liquid-absorbant (that is, rich gas body) is referred to containing higher than minimum The liquid-absorbant of the gas that a certain amount of Jing of concentration absorbs.The gas that these Jing absorb gradually is gone during regeneration technology Remove.No longer from the time point of liquid-absorbant desorption gas (that is, the Cmin of the gas that Jing absorbs), liquid-absorbant quilt Referred to as " lean " (that is, depleted gas).At this moment, the gas that liquid-absorbant may be also absorbed containing fairly large number of Jing.Therefore, In this application, the liquid-absorbant of the gas for absorbing containing a certain amount of Jing higher than lean absorbent concentration is referred to as rich solution Body absorbent.
According to an aspect of the invention, there is provided a kind of method from rich gas liquid stripping gas, methods described bag Include：
Rich gas liquid is heated in desorption unit with from rich gas liquid desorption gas, and is formed and is included gas and steaming First product stream of gas, and including the second product stream of depleted gas liquid；And
At least one of the following step：
Make the first product stream contact with vapor permeable film condensers to pass through permeable membrane interface by least one of steam Point remove from the first product stream, the first product stream passes through film condensers and with the rich gas liquid into desorption unit at least A part of heat-shift is heating rich gas liquid stream；And/or
The second product stream is contacted with vapor permeable film evaporator with by the membrane interface of permeable membrane by steam at least A part is removed from the second product stream, and the separated part of the second product stream is back to desorption unit.
In one embodiment, the step of making the first product stream be contacted with rich gas liquid stream is included the first product stream In steam be condensed into liquid to form a part for rich gas liquid stream.Contact and condensing steps are preferably in film condensers Middle enforcement.Can adverse current or concurrent flow the first product stream and rich gas liquid are incorporated in film condensers, but adverse current is Preferred option.In this embodiment, steam is condensed when which passes through membrane interface and enters rich gas liquid entrance stream.
In the other embodiments that can be combined with many aspects of other embodiments of the present invention, by steam The step of at least a portion is removed from the second product stream includes：
By at least a portion of second product stream of membrane interface flash distillation of film evaporator.
After flashing, the second product stream (wherein flash vapors are removed) is supplied to heat exchanger to heat rich gas body At least other part of liquid flow is so that at least other part returns to desorption unit.
Preferably, include the step of rich gas liquid in heating desorption unit and steam heat exchange or contact.
The gas can be uncondensable gas.Present invention is preferably adapted for use with being selected from CO2、H2S or SO2Composition Group gas, and rich gas liquid and depleted gas liquid include the gas absorbent of the group selected from the following composition： Ammonia, alkanolamine, alkylamine, amino acid, its salt, inorganic base and its mixture.
For film condensers and evaporator effects, the film preferably can steam blanket and more preferably steam choosing thoroughly Selecting property film.The vapor permeable film of at least one of film condensers and film evaporator is hydrophobic or hydrophilic.When film it is cold The membrane interface of condenser is hydrophobic and during by rich gas liquid and gaseous state the first product flow separation, the pressure in rich gas liquid Power is more than the pressure in gaseous product stream.Additionally, when the membrane interface of film evaporator is hydrophobic and by the second product of gaseous state When stream returns flow separation with liquid regeneration device, the pressure that liquid is returned in stream is preferably more than the pressure in the second product stream of gaseous state Power.
In operation, it is preferable that the temperature of desorption unit is about 80 DEG C to about 200 DEG C, and the pressure in desorption unit It is about 0.5 bar to about 15 bars.
According to another aspect of the present invention, there is provided a kind of equipment for from rich gas liquid stripping gas, it is described Equipment includes：
Desorption unit, the desorption unit for from rich gas liquid desorption gas forming including gas and steam One product stream, and including the second product stream of depleted gas liquid, the desorption unit includes that rich gas liquid entrance, first produce Stream outlet and the second product flow export；And
At least one of the following
Film condensers, the film condensers include
For receiving the entrance of the first product stream and rich gas liquid stream
The membrane interface of vapor permeable, steam are transferred to rich gas liquid stream from the first product stream through the membrane interface,
With the outlet of the rich gas liquid fluid communication of desorption unit, and for steam reduce the first product stream Outlet；And
Film evaporator, the film evaporator include
For receiving at least one of entrance of the second product stream；The membrane interface of vapor permeable, steam pass through the film Interfacial migration is with from the second product flow separation vapor portion；And the outlet of the second product stream reduced for steam.
Preferably, the equipment includes both film condensers and film evaporator, and preferably also includes to desorption unit The heating unit of heat is provided.Can adverse current or concurrent flow the first product stream and rich gas liquid stream are received into film condensers In, but adverse current is preferred option.
Desorption unit is operated together preferably in combination with absorptive unit and heat-exchange device, and the absorptive unit is used to contact lean Liquid-absorbant gas stream to produce rich gas liquid stream, the heat-exchange device for the second product stream for reducing in steam with The heat transfer between a part for the rich gas body stream of absorptive unit.Steam reduce the second product stream at least a portion with Absorptive unit is in fluid communication.Rich gas body stream from heat-exchange device is directly or indirectly in fluid communication with desorption unit.
Preferably, operation of the permeable membrane of film condensers and/or film evaporator in corresponding condenser or evaporimeter Gas is not through under temperature and pressure substantially.The film can be selective membrane and preferably, and film condensers and/or film steam The film for sending out the membrane interface of device is made up of hydrophobic material.Or, the film of the membrane interface of film condensers and/or film evaporator be by Hydrophilic material is made, but different operating pressures are needed in condenser and evaporimeter.
Advantageously, the invention allows to liquid is greatly lowered during (PCC) technique is captured after the burning based on amine The thermal demand of absorbent regeneration.Therefore, the present invention is just solved in the case where returning to the liquid-absorbant of replacement One of major defect of prior art PCC.
By way of example and refer to the attached drawing, by the other aspect and previous paragraph of the clear present invention in from the description below Described in many aspects other embodiments.
Brief description
Fig. 1 is the CO of the use chemical absorbent according to prior art2The process chart of recovery；
Fig. 2 is the diagram of one embodiment of the invention, is shown for from rich gas liquid absorbent desorption gas Gas desorption unit, the unit include reclaim heat energy used by hot transfer equipment；
Fig. 3 is the schematic diagram for shifting the operation of the hydrophobic porous film of vapor (condensation mode)；And
Fig. 4 is the schematic diagram for shifting the operation of the Hydrophilized porous membrane of vapor (condensation mode).
The detailed description of embodiment
The regeneration of liquid-absorbant is present invention can be suitably applied to, the liquid-absorbant contains in the temperature lower than regeneration temperature The gas absorbed from the mixture of feed gas under degree, under the regeneration temperature, these gas from liquid absorbent are removed. Gas to be removed is typically the sour gas of so-called similar carbon dioxide and hydrogen sulfide, but the technique is applicable to appoint What gas-liquids absorbent combination, wherein GAS ABSORPTION is thermal reversion.Liquid-absorbant will be typically evaporable containing holding Component such as water or methyl alcohol, and cause one or more component of the gas sorption capability increase of liquid-absorbant.Component this A little types depend on gas to be removed.For sour gas remove, these components be typically organic base such as amine, including ammonia, MEA and other alkanolamines；And inorganic base such as carbonate and phosphate.
Therefore, in one embodiment, the present invention relates to one kind is for carrying out heat integration liquid suction by gas desorption Receive the technique and equipment of agent regeneration.The generating apparatus again can include
For the entrance of rich gas liquid absorbent, the rich gas liquid absorbent is containing a certain amount of to be removed The liquid-absorbant of the gaseous component of absorption,
- for the outlet of depleted gas liquid-absorbant, the depleted gas liquid-absorbant is treating containing decrement The liquid-absorbant of the gaseous component of the absorption for removing,
- for the outlet of the gaseous component that desorbs from liquid-absorbant and steam,
- there is conduit, heat exchanger, the system of contact arrangement, the system mainly realizes liquid-rich absorbent and lean solution In the counter-current operation of both body absorbent and gaseous component to be removed, but each area being described below, it is not necessary. The equipment can also include；
- steam produces area, wherein providing desorption gas and maintaining needed for heat energy necessary to the driving force of gas desorption Steam (typically steam) is generated by the boiling of liquid-absorbant, preferred reboiler,
- one or more gas desorptions and condensing zone, wherein steam are condensed into liquid absorption in gas-liquid contact device Agent, so as to provide from the energy needed for liquid-absorbant desorption gas,
- one or more hot transition ranges, wherein sensible heat amount are transferred to liquid-rich absorbent from lean liquid-absorbant, and/ Or the steam produced from lean liquid-absorbant is condensed, so as to potential heat is transferred to rich absorbent.This preferably heat is handed over Changing device.
The equipment includes at least one of one or more steam transition ranges, and wherein steam is inhaled from lean liquid via film Receive agent (the second product stream) and be transferred to liquid-rich absorbent (rich gas liquid), the film substantially prevents liquid-absorbant and desorption The transfer of gas,
- one or more vapor condensation zoYles, wherein steam are via film from the mixed of desorption gas and steam (the first product stream) Compound is transferred to liquid-rich absorbent (rich gas body stream), and the film substantially prevents liquid-absorbant and desorption gas in either direction On transfer, and
- one or more hot transition ranges, wherein heat are via evaporation or conduct from lean liquid-absorbant (the second product stream) It is transferred to cooling medium.
The advantage of embodiments hereinbefore is：For gas phase or vapor phase and compressor is not needed, and alternatively only made With liquid pump as slewing.
Technological process shown in Fig. 2 is illustrated is used for heat integration liquid-absorbant according to above-described embodiment One example of the equipment of regeneration.The example is related to by vapor permeable and the film of impenetrable liquid is condensed and evaporated back and forth Receive potential heat.
Fig. 2 provides the diagram of one embodiment of the invention.Fig. 2 is shown including for reclaiming the heat transfer of heat energy Equipment, from the gas desorption unit of rich gas liquid absorbent desorption gas.
The equipment of Fig. 2 includes regenerator (or gas desorption unit or stripper).Entered by first entrance 25 and/or second Mouth 24 is incorporated into rich gas liquid absorbent in regenerator.In regenerator 10 and associated reboiler 12, rich gas body is made Liquid-absorbant with contacted by heat steam (such as steam).This causes gas (such as CO2) desorb from rich gas liquid, so as to Offer includes first product stream 13 and the second product stream 14 including depleted gas liquid of gas and steam.Enter from the first steam Mouth 15 and/or the second vapour inlet 16 are incorporated into steam in regenerator.First vapour inlet is connected to liquid using heat energy Change on the reboiler unit 12 of steam.Second vapour inlet 16 is connected on film evaporator 17.
Depleted gas liquid 14 leaves container 10, and a part of depleted gas liquid 14a is passed to reboiler, is boiling again At device, the depleted gas liquid is provided heat energy and changes into steam.Pass through the first vapour inlet 15 afterwards by the steam It is incorporated in regenerator 10 again.Another part of depleted gas liquid 14b is passed to film evaporator 17.Due to this part 14b Through film evaporator 17, on whole film, there is the difference of the partial pressure of steam.This partial pressure difference causes of depleted gas liquid Divide 14b conversions or flash distillation to form flash vapors.Flash vapors (steam) through film evaporator 17 membranous wall 18 and via Two vapour inlets 16 are incorporated in regenerator 10 again.Heat exchanger is passed through after the unvaporized portion 19 of depleted gas liquid 20, wherein heat is transferred to a part of 21a of the rich gas body stream 21 from gas absorber (not shown), the part 21a is transferred to the second entrance 24 of regenerator 10.After through heat exchanger 20, after depleted gas liquid 23, suction is passed to Receive device (not shown) to be re-filled with gas.
The first product including the gas and steam (such as steam) for having desorbed from rich gas liquid is extracted from regenerator 10 Stream 13, and first product stream 13 is transferred to into film condensers 22.Film condensers 22 include the membrane interface 24 of vapor permeable. It is the rich gas liquid absorbent of a part of 21b of stream from absorber on the side of membrane interface 24, and membrane interface 24 It is the first product stream 13 on opposite side.As the first product stream 13 passes through film condensers 22, so steam passes through film 24 and enters Enter in the rich gas liquid absorbent come the 21b that flows automatically.Some or substantially all steam can in this way from the first product stream 13 remove.This generates the main high-purity product 25 for including desorption gas.As stated, steam passes through film 24 and enters In the rich gas liquid absorbent of gravity flow 21b.The steam is condensed into liquid, so as to be released in before entering into regenerator 10 The heat energy of the rich gas liquid of heating.Then the rich gas liquid being heated is incorporated in desorber by first entrance 24.
Embodiment shown in Fig. 2 covers for shifting and reclaiming two main positions of potential heat.
I () recovers energy from the lean hot liquid absorbent 14,14a, 14b of the bottom for leaving regenerator 10.It is single into desorption Generally there is significant difference between first 10 rich absorbent and the temperature of the lean absorbent for leaving regenerator, because temperature contrast It is to be determined by the vapor-liquid balance under setting pressure.As the mode for obtaining more preferable recuperation of heat, from the flash distillation of lean solvent Steam directly can be transmitted back in regenerator.It is conceptive at this, it is not necessary to steam compressed, and simply by vapor permeable Film 18 is by steam raising in regenerator.Preferably the film is placed in regenerator to provide short flow path, from And avoid the demand for recompressing.As evaporation process has very high switching rate, by CO2Re-absorption is to lean liquid-absorbant In be limited.In addition, the presence of film 18 and its loose structure can aid in restriction CO2Re-absorption in lean solvent, because Extra diffusion barrier be act as the film.
(ii) as illustrated in figure 2 by the CO for leaving regenerator 102/H2O gases stream 13 is with the rich absorbent 21b's for entering Between a part, heat-shift is reclaiming heat.Generally, the vapor in the stream is only condensed, and energy is in cooling current In be pulled away.Within the concept of the invention, recuperation of heat is realized via the condensation of vapor is carried out by vapor permeable film 26. The presence of envelope barrier 26 herein can also aid in restriction CO2Re-absorption is in rich solvent.
Using the advantage for shifting the film of vapor (by evaporating or condensing) from the steam carried out by envelope barrier Directly contact between liquid.
Two kinds of heat recovery methods are directed to sensible heat and potential recuperation of heat to by regenerator 10, condenser 22 and lean/rich Heat exchanger 20 composition it is total during.Which is related to by evaporating and condensing the transfer of the vapor for carrying out, and ultimately results in potential Heat is from a phase transfer to another phase.This can be completed in more effective, controllable and selective mode using the film of porous. Various polymer films obtained by existing and inoranic membrane (porous and non-porous), they can effectively accomplish this point.
For condensation mode, two kinds of film concepts in Fig. 3 and Fig. 4, are shown.For evaporation profiles, the transfer of vapor is only Reversible.
In figure 3, (CO2/H2In O streams 13) vapor is via hydrophobic porous film and colder liquid-rich absorbent stream (i.e. 21b in Fig. 2) is contacted.Pressure on liquid-absorbant side should be higher than that the pressure on gas side, and otherwise gas only can permeate Through hole and bubbling pass through liquid.Such case to be avoided, because gas and being sufficiently mixed for liquid may result in CO2Turn Move on in absorption liquid, this is undesirable.The condensation of vapor in liquid-rich absorbent makes it possible to reclaim potential heat.It is right In perforated membrane, absorb liquid and be not allowed in fenestra, until beyond breakthrough pressure.This is by pressing on aperture, whole film The impact of the interaction of difference and absorption liquid and membrane material.These superficial phenomena are described by Laplace equations：
Δ p=-2 (Y/r) .cos Θ (1)
Wherein
△p=PLiquid-PGas：Pressure differential [N/m2]
Y ：The surface tension [N/m] of liquid
r ：Pore radius [m]
θ ：Contact angle
If contact angle is more than 90 ° and pressure differential is limited for given aperture, fenestra will not be wetted.
It is non-polar polymer suitable for the aqueous membrane material for absorbing liquid, such as polypropylene, polyethylene and polytetrafluoroethyl-ne Alkene.Due to surface tension as temperature reduces, breakthrough pressure is reduced with the increase of temperature.Film will be with meaning to go out The pore-size distribution of existing some wettings.Once fenestra is wetted, some absorb liquid and just will penetrate through film and reach gas side.So And, a small amount of Liquid Penetrant (while not wishing to) and be not considered as it is serious because the transfer of vapor and the recovery of heat are not Can be affected by such case.Liquid will only eventually arrive at regenerator, and it will not be lost in.
Figure 4 illustrates the second configuration.In such a mode, film is hydrophilic, and by capillary force, fenestra It is wetted.When liquid lateral pressure is only slightly higher than gas side pressure, liquid can comparatively easy penetrate through film.By in gas Apply the pressure higher than hydraulic fluid side on side, it is possible to reduce Liquid Penetrant.As film is wetted, bubble point is that gas will start to ooze Can be determined by herein below through the point residing for film thoroughly：
Δ p=2 (Y/r) (2)
Wherein：
△p=PGas-PLiquid：Pressure differential [N/m2]
Y：The surface tension [N/m] of liquid
r：Pore radius [m]
If pressure differential exceedes the value that equation 2 is provided, bubbling is passed through film and is entered in liquid by gas.This is not It is desired.When liquid lateral pressure is slightly above gas side pressure, then liquid would be possible to comparatively easy penetrate through film.
It is hydrophilic polymer suitable for the aqueous membrane material for absorbing liquid, such as polysulfones, polyether sulfone, polyvinyl alcohol and polyamides Amine and ceramic material or metal；It is generally used for the membrane material that liquid filters purpose such as micro-filtration, ultrafiltration, nanofiltration and counter-infiltration. It is same in the configuration of this film, a small amount of liquid-absorbant infiltration or reveal (while not wishing to) and be not considered as it is important, because The recovery of transfer and heat for vapor will not be affected by such case.Liquid will only eventually arrive at regenerator, and it Will not be lost in.This Liquid Penetrant may go through pin hole, breach (imperfection) and aperture and be far longer than nominal pore The region in footpath occurs.Therefore, the Test Liquid Permeability of Core of the 10% of up to total stream is considered as acceptable, but is not desired.
Under the condensation of the technique and evaporation profiles, it is beneficial to, limit CO2Branch back in liquid-absorbant, because Contribute to resorbent driving force to exist.Condensation or evaporation process are significantly faster than CO2The process in liquid is absorbed, and And restriction CO can be produced2Resorbent advantage.However, either condensation portion or evaporation section, film should all show High vapour permeability with avoid reduce steam transfer rate.Therefore steam permeability should be higher than that 3 10-7mol/m2SPa is (about 1000GPU), preferably higher than 3 10-6mol/m2SPa (about 10,000GPU) and ideally be higher than 3 10-5mol/m2sPa (about 100,000GPU).
The present invention is typically described for removing removing carbon dioxide from rich gas absorbent.Rich gas absorbent can be alkalescence The aqueous solution (inorganic salts, including the amine of amino-acid salt).Can be under typical regeneration temperature (between i.e. 100 DEG C and 150 DEG C) The rich gas absorbent of regeneration.CO2Source be from natural gas flow, flue gas, biogas, shale gas, coal bed gas, industrial gas Body, air etc..
Although the present invention removes CO with reference to from rich gas absorbent2Extensive description, but those skilled in the art are carried out It will be understood that, the apparatus and method of the present invention are applicable to remove other gases from rich gas absorbent.For example, methods described and Equipment can be used for removing H2S、SO2Or general other sour gas in waterborne liquid absorbent are absorbed from gas stream. Additionally, methods described and equipment can be used for other and separating and such as carrying out paraffin/olefin separation, use using silver nitrate aqueous solution Copper chloride solution containing ammonia carries out carbon monoxide separation, volatile compound to be used to wave gas from liquid stream with wherein steam The separation of the waste water for send out/desorbing.Stripping steam is also possible to other condensable components containing steam pressure similar to water.It is real The scope for applying example is that, from the ammonia and methyl alcohol with water complete miscibility to the less miscible component such as toluene based on hydrocarbon, this depends on liquid The type of body absorbent.
Embodiment
Liquid-absorbant used in this analysis is the 30%MEA aqueous solution, and it is used as benchmark in many researchs. In the liquid regeneration technique of standard, heat energy is provided via reboiler, so as to cause 120 DEG C of bottom temp.This will cause to generate Stripped vapor, the stripped vapor will be travelled upwardly in regenerator.Some vapor will be condensed in liquid-absorbant, so as to carry For discharging CO from the liquid-absorbant downwardly through regenerator2Required heat.Stripped vapor will carry CO2It is upward through Tower.The water saturated CO under the head temperature of regenerator2Product will leave tower, typically 0.6 ton of steam/ton CO2.Steam The heat that vapour is removed within the condenser and condenses is pulled away in cooling water.Which constitute the heat energy of liquid regeneration technique A part for demand.Second contribution may be from the need that the bottom from the top of regenerator to regenerator is heated to liquid-absorbant Ask.This typically loads determination by wait press operation (isobar operation) and the common liquid-absorbant of regenerator, and Typically, liquid-absorbant needs to heat 15K when downwardly through tower.Final contribution carrys out self destruction CO2Inhale with liquid Receive agent between key needed for energy and actually by CO2Energy needed for desorbing from liquid-absorbant.This depends on liquid Body absorbent, and for MEA, typically 1.7GJ/ tons CO2。
The general introduction of the physical characteristic and technological condition of regeneration of liquid-absorbant is given in table 1.
Table 1：Physical parameter and technological condition of regeneration
Physical characteristic or process conditions Value
CO2With reference to energy [GJ/ ton CO2] 1.7
Heat of evaporation [GJ/ ton H2O] 2.2
Volumetric heat capacity amount [the MJ/m of liquid-absorbant3K] 4
Flow rate [the m of particular liquid absorbent3/ ton CO2] 20
The inlet temperature [DEG C] of lean/rich heat exchanger-rich absorbent 55
The bottom temp [DEG C] of regenerator 120
The head temperature [DEG C] of regenerator 105
The pressure [bar] of regenerator 1.8
H at the top of regenerator2O and CO2Than [ton H2O/ ton CO2] 0.6
It is desirable that, the thermal demand of the regeneration of liquid-absorbant can be by introducing one for any liquid-absorbant Or two film applications are significantly reducing.This is realized by herein below：
- by the film condensers on the top of regenerator by vapor and potential heat recovery in rich absorbent, so as to Cause H2O and CO2Than equal to 0.1
- vapor for leaving the lean absorbent of bottom is transferred in regenerator, so as to cause potential heat recovery to again In raw tower.
Expect that the potential heat recovery method for combining makes the temperature of liquid-absorbant lift (temperature lift) 5K is down to from 15K
By synchronized development, the feature of desirable for liquid absorbent it is alternatively improved, so as to cause lower CO2With reference to energy Amount and higher attainable CO2Load.Two kinds of effects both contribute to the energy requirement of liquid-absorbant regeneration.
Table 1 provides standard technology, heat integration technique and using base in the heat integration technique of the liquid-absorbant of improvement The comparison of the physical characteristic be given in table 1 and the temperature of technological parameter and steam composition.
Table 2：Comparison between standard technology and heat integration technique
As the analysis result that presented in table 2 indicate the improvement of thermal demand 50% it is available in one's power in the range of absolute value be 2GJ/ ton CO2Thermal demand realizing.
It will be understood that, text is extended to the present invention of definition disclosed in this specification or accompanying drawing is mentioned or obvious from them Two or more all alternative combinations of the single feature for drawing.All these various combinations constitute the various of the present invention Alternative aspect.

Claims (24)

1. a kind of method from rich gas liquid stripping gas, methods described include：
Rich gas liquid is heated in desorption unit to desorb the gas from the rich gas liquid, and formed include it is described First product stream of gas and steam, and including the second product stream of depleted gas liquid；
First product stream is contacted with vapor permeable film condensers with by permeable membrane interface by the steam at least A part is removed from first product stream, and first product stream passes through the film condensers and desorbs list with into described At least a portion heat-shift of the described rich gas liquid of unit is heating the rich gas liquid stream；With
Second product stream is made to contact with vapor permeable film evaporator with the membrane interface by the permeable membrane by the steaming At least a portion of gas is removed from second product stream, and the separated part of second product stream is back to described Desorption unit；
It is wherein described to include first product stream the step of first product stream is contacted with vapor permeable film condensers In steam be condensed into liquid to form a part for the rich gas liquid stream.
2. the method for claim 1, wherein the contact and condensing steps are implemented in the film condensers.
3. method as claimed in claim 2, wherein steam pass through the membrane interface at which and enter into the rich gas liquid It is condensed during mouth stream.
4. the method for claim 1, wherein described at least a portion by the steam is from the second product diffluence Except the step of include：
By at least a portion of second product stream of membrane interface flash distillation of the film evaporator.
5. method as claimed in claim 4, which also includes for second product stream being supplied to heat exchanger described to heat At least other part of rich gas liquid stream is so that at least other part returns to the desorption unit.
6. the method for claim 1, wherein including and steam exchanged heat the step of the heating rich gas liquid Amount.
7. method as claimed in claim 6, wherein the film is can steam blanket thoroughly.
8. the method as any one of claim 1～7, wherein the gas is selected from CO2、H2S、CO、C2H4、C3H6、 C4H8、O2、NO2Or SO2The group of composition.
9. the method as any one of claim 1～7, wherein the temperature of the desorption unit is 80 DEG C to 200 DEG C.
10. the method as any one of claim 1～7, wherein the pressure of the desorption unit is 0.5 bar to 15 bars.
11. methods as any one of claim 1～7, wherein the rich gas body fluid body and the depleted gas liquid bag Include the gas absorbent of the group selected from the following composition：Ammonia, alkanolamine, alkylamine, amino acid, its salt and its mixing Thing.
12. methods as any one of claim 1～7, wherein at least in the film condensers and film evaporator The individual vapor permeable film is hydrophobic.
13. methods as any one of claim 1～7, wherein the membrane interface of the film condensers is hydrophobic, and And by rich gas liquid and gaseous state the first product flow separation, the pressure in the rich gas liquid is more than in the gaseous product stream Pressure.
14. methods as any one of claim 1～7, wherein the membrane interface of the film evaporator is hydrophobic, and And the second product stream of gaseous state and liquid regeneration device are returned into flow separation, the liquid returns pressure in stream more than the gaseous state the Pressure in two product streams.
A kind of 15. equipment for from rich gas liquid stripping gas, the equipment include：
Desorption unit, the desorption unit for from the rich gas liquid desorption gas being formed including the gas and steam The first product stream, and including the second product stream of depleted gas liquid, the desorption unit include rich gas liquid entrance, One product flow export and the second product flow export；
Film condensers, the film condensers include
For receiving the entrance of first product stream and rich gas liquid stream,
The membrane interface of vapor permeable, steam are transferred to the rich gas liquid from first product stream through the membrane interface Stream,
With the outlet of the rich gas liquid fluid communication of the desorption unit, and for steam reduce the first product stream Outlet；With
Film evaporator, the film evaporator include
For receiving at least one of entrance of second product stream；The membrane interface of vapor permeable, steam pass through the film Interfacial migration is with from the second product flow separation vapor portion；And the outlet of the second product stream reduced for steam.
16. equipment as claimed in claim 15, which is also included for the heating unit to desorption unit offer heat.
17. equipment as claimed in claim 15, which is also included for contacting lean liquid-absorbant gas stream to produce the richness The absorptive unit of gas liquid stream.
18. equipment as claimed in claim 17, which also includes the second product stream for reducing in the steam and from institute A heat-exchange device of heat transfer between a part for the rich gas body stream for stating absorptive unit, the second product that the steam is reduced At least a portion of logistics is in fluid communication with the absorptive unit.
19. equipment as claimed in claim 18, wherein from the rich gas body stream and the desorption unit of the heat-exchange device Directly or indirectly it is in fluid communication.
20. equipment as any one of claim 15 to 19, wherein the film condensers and/or film evaporator are comprising partly Permeable membrane, half permeable membrane are substantially not through gas under the operation temperature and pressure of corresponding condenser or evaporimeter Body.
21. equipment as claimed in claim 20, wherein the film is can steam blanket thoroughly.
22. equipment as claimed in claim 15, wherein the film of the membrane interface of the film condensers and/or film evaporator is by dredging Made by water-based material.
23. equipment as claimed in claim 15, wherein the film of the membrane interface of the film condensers and/or film evaporator is by parent Made by water-based material.
24. equipment as described in claim 22 or 23, wherein the film is provided with vapor permeable coating.
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